CN113019329B - Method for modifying MOFs material by low-temperature plasma and application - Google Patents
Method for modifying MOFs material by low-temperature plasma and application Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 116
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- 238000000034 method Methods 0.000 title claims abstract description 40
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- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
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- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 2
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- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 description 2
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 2
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- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 2
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- 238000011065 in-situ storage Methods 0.000 description 2
- 229960000453 malathion Drugs 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229940079888 nitenpyram Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- QYMMJNLHFKGANY-UHFFFAOYSA-N profenofos Chemical compound CCCSP(=O)(OCC)OC1=CC=C(Br)C=C1Cl QYMMJNLHFKGANY-UHFFFAOYSA-N 0.000 description 2
- QHMTXANCGGJZRX-WUXMJOGZSA-N pymetrozine Chemical compound C1C(C)=NNC(=O)N1\N=C\C1=CC=CN=C1 QHMTXANCGGJZRX-WUXMJOGZSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
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- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- 230000001094 effect on targets Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 229940038487 grape extract Drugs 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
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- 238000003746 solid phase reaction Methods 0.000 description 1
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- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a method for modifying MOFs material by low-temperature plasma and application, wherein argon is led to pass through a liquid modifier under the condition of air tightness, so that saturated steam carrying the liquid modifier in the argon is subjected to low-temperature plasma discharge reaction with the MOFs, the liquid modifier is an organic reagent which is liquid at room temperature or an organic reagent which is liquid under the heating condition of an oil bath at the temperature of not higher than 100 ℃, the low-temperature plasma discharge reaction is carried out under the conditions of room temperature and normal pressure, the discharge power is 0.5W-1.5W, and after the plasma reaction is finished, the functionalized and modified MOFs are obtained. The method has the advantages of simple equipment, mild conditions, low carbon and environmental protection, and the obtained functionalized and modified MOFs material can be used as a solid phase extraction adsorbent and can be efficiently and circularly stably applied to selective adsorption and enrichment of pesticide molecules in a complex matrix.
Description
Technical Field
The invention relates to the technical field of metal organic framework material preparation, in particular to a method for modifying MOFs material by low-temperature plasma and application thereof.
Background
Metal Organic Frameworks (MOFs) are one of the very colorful star materials in the field of advanced materials for over 20 years, and compared with the traditional porous solid phase materials, the MOFs have unique and significant advantages, including high or even ultra-high specific surface area and porosity, regular pore channel structures, modifiability of pore channel environment, designability of structures and controllability of properties. In the field of analytical chemistry, MOFs is a novel solid phase extraction adsorption material with great potential, a regular pore structure can exert a size effect and shape selectivity, and a large number of metal nodes and organic connecting groups can reversibly adsorb object molecules through weak intermolecular interaction, so that the aims of reversibly adsorbing and enriching target molecules and recycling an adsorbent are fulfilled.
Separation and enrichment of trace residual pesticide molecules in a complex system are core problems in the field of pesticide residue analysis and environmental protection, and realization of high-selectivity adsorption of target molecules through efficient solid-phase extraction is a research hotspot at present, wherein design and synthesis of a solid-phase extraction adsorbent are the core. The construction of multiple non-covalent interactions between the adsorbent surface and the target pesticide molecule is an important strategy to achieve specific adsorption. For MOFs materials, the introduction of target functional groups on numerous organic connecting groups of MOFs through chemical reactions to realize precise functional modification of MOFs is a difficult problem and a hot spot of functional research and application of the MOFs materials at present. In the aspect of adsorption separation, the functionalized and modified MOFs cooperate with metal nodes, organic connecting groups, characteristic pore channel structures and the like of the MOFs through introduced target functional groups, so that noncovalent interaction, such as pi-pi interaction, hydrophobic interaction, electrostatic interaction, hydrogen bond interaction, halogen bond interaction and the like, occurs between the MOFs and target pesticide molecules, and the cooperation among multiple noncovalent interactions can lead the MOFs to specifically recognize and selectively adsorb the pesticide molecules, so that the target pesticide molecules are successfully separated from the substrates where the MOFs are located.
Currently, the functionalization modification strategies for MOFs are classified into in-situ synthesis functionalization MOFs strategies and post-synthesis functionalization modification strategies. The strategy of in-situ synthesis of functionalized MOFs is limited by the problems of solubility, thermal stability, chemical stability of organic ligands, compatibility of functionalized groups and the like, so that the range of functionalized modification is extremely limited. The post-synthesis functionalization modification strategy is mainly based on covalent modification of organic connecting groups in MOFs at present, strict requirements are imposed on the electrical property, the space structure and the like of free functional groups and organic connecting groups on the organic connecting groups, and the functionalization modification range is very narrow. In a macroscopic view, the current functionalization modification strategies for MOFs are all based on the traditional chemical reaction and are limited by reaction thermodynamics and kinetics, and the functionalization modification regulation space is limited; on the other hand, the common problems of the existing modification strategies are that the reaction is carried out in a solution system, the using amount of an organic solvent is large, the reaction conditions are generally harsh, the requirement on equipment is high, a functionalized reagent is expensive, the functionalized modification cost is high, and the real practical application is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for modifying MOFs material by low-carbon and environment-friendly low-temperature plasmas and application thereof, wherein the method has the advantages of simple equipment, mild reaction conditions, and capability of separating and enriching pesticide molecules in a complex matrix by using the obtained functionalized modified MOFs material as a solid-phase extraction adsorption material, and has the characteristics of high efficiency, high selectivity, stable cycle and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for modifying MOFs materials by low-temperature plasmas comprises the following steps: and under the condition of air tightness, passing argon through a liquid modifier, and enabling saturated steam carrying the liquid modifier with the argon to perform low-temperature plasma discharge reaction with MOFs, wherein the liquid modifier is an organic reagent which is liquid at room temperature or an organic reagent which is liquid under the heating condition of an oil bath at the temperature of not higher than 100 ℃, the low-temperature plasma discharge reaction is performed under the conditions of room temperature and normal pressure, the discharge power is 0.5W-1.5W, and after the plasma reaction is finished, the functionalized and modified MOFs are obtained.
In the method for modifying MOFs materials by using low-temperature plasma, preferably, the MOFs comprise one or more MOFs materials in an MIL series, a UiO series, a ZIF series and a HKUST series.
In the method for modifying the MOFs material by using the low-temperature plasma, preferably, the organic reagent comprises one or more of phenol, alcohol, organic amine, carboxylic acid and hydroxycarboxylic acid.
In the method for modifying the MOFs material by using the low-temperature plasma, preferably, the time of the low-temperature plasma discharge reaction is 20min to 60min.
Preferably, the low-temperature plasma discharge mode of the method for modifying the MOFs material includes one of glow discharge, dielectric barrier discharge and pulse discharge.
In the method for modifying the MOFs material by using the low-temperature plasma, the flow rate of the argon is preferably 20mL/min to 100mL/min.
Preferably, after the plasma reaction is finished, the MOFs material is dried in vacuum at 120-150 ℃ overnight.
As a general technical concept, the invention also provides application of the functionalized modified MOFs prepared by the method for modifying the MOFs material by using the low-temperature plasma as a solid-phase extraction adsorbent in adsorption and enrichment of pesticide molecules in a complex matrix, namely high-efficiency and high-selectivity adsorption and enrichment of the pesticide molecules in the complex matrix.
In the above application, preferably, the complex substrate comprises fruits, vegetables, grains, meat, eggs, aquatic products, soil or environmental water, and the pesticide molecule comprises one or more of an insecticide, a bactericide and a herbicide.
In the invention, argon is firstly introduced into a double-mouth flask containing a liquid modifier through a gas guide pipe (gas inlet pipe), the gas inlet pipe extends below the liquid level of the liquid modifier, and a gas outlet pipe is positioned above the liquid level, so that the argon passing through the double-mouth flask carries saturated steam of the modifier to enter a plasma reaction area of low-temperature plasma equipment.
In the invention, the functionalized and modified MOFs material is applied to the solid-phase extraction of trace pesticide molecules in a complex matrix, and the evaluation conditions are as follows: adding 2mg of functionalized MOFs into a matrix extracting solution (5 g of matrix and 20mL of extracting solution) with pesticide concentration of 5mg/kg at room temperature, and performing vortex extraction for 1min.
The main principle of the invention is as follows:
argon carries saturated steam of an organic modifier into a plasma reaction zone, a large number of free radical species are generated under the condition of low-temperature plasma discharge, the free radicals are very active and can generate free radical substitution reaction with aromatic organic connecting radicals of MOFs (including MOFs materials stable to water and air such as MIL series, uiO series, ZIF series and HKUST series), and the reaction is similar to Friedel-crafts substitution reaction. After the low-temperature plasma reaction lasts for a period of time, the MOFs are modified into a target functionalized structure. Due to the thermodynamic nonequilibrium characteristic of the low-temperature plasma, although a large amount of high-activity free radical species can be generated in the discharge reaction process, the macroscopic temperature presented by the whole reaction is room temperature, the reaction condition is very mild, and the integrity of the characteristic crystal structure and the pore structure of the MOFs can be effectively ensured without any damage.
The MOFs functionalized and modified by low-temperature plasma is used as a solid-phase extraction adsorbent, and various non-covalent interactions can be generated with guest molecules through modified functional groups on the MOFs and cooperation of an organic connecting group and metal ions, wherein the non-covalent interactions include electrostatic interactions, nonpolar interactions (van der Waals acting force), polar interactions (hydrogen bonding interactions, pi-pi interactions, dipole interactions, halogen bonding interactions and the like), hydrophobic interactions and the like. Meanwhile, the high-efficiency high-capacity adsorption and enrichment effect on target adsorption molecules is achieved by combining developed inner surfaces, pore channel structures and active adsorption sites of MOFs. The adsorbent based on reversible adsorption can be recycled after being eluted and regenerated.
The invention provides a method for preparing functional modified MOFs, which is based on the thermodynamic nonequilibrium characteristic of low-temperature plasma reaction, under normal temperature and normal pressure, takes argon which is easily activated into a metastable state under the condition of low-temperature plasma as carrier gas, carries an organic modifier containing a target functional group to enter a plasma discharge reaction zone, and the organic modifier is activated under the condition of low-temperature plasma to generate high-activity free radical species which perform free radical substitution reaction with an aromatic organic connecting radical of the MOFs, so that the target functional group is directly introduced into the MOFs, and the functional modified MOFs is prepared by one-step reaction. The MOFs is functionalized and modified by using a low-temperature plasma technology, high-temperature activation reaction molecules are not needed, chemical thermodynamics is not needed, a modifier is cheap and easy to obtain, the selection range is very wide, the reaction conditions are mild, the atom utilization rate is high, the requirements on equipment conditions and process operation are simple, high efficiency and energy conservation are realized, and the concept of green chemistry and sustainable development is met. The functionalized modified MOFs obtained after the reaction is used as a solid phase extraction adsorbent, and can be used for efficiently and selectively enriching and extracting trace pesticide molecules in a complex matrix based on the cooperation of various non-covalent interaction forces between the functionalized modified MOFs and a target object.
Compared with the prior art, the invention has the advantages that:
(1) The invention adopts the low-temperature plasma technology, so that the functionalization modification of MOFs can be realized under mild conditions, high temperature and high pressure are not needed, the problems of MOFs crystal structure damage, pore collapse damage and the like can be effectively prevented, the product quality is ensured, and meanwhile, the process is simple and environment-friendly.
(2) The method can realize the functionalized modification of MOFs under the gas-solid phase reaction condition, avoids using a large amount of organic solvents, and has green and high-efficiency reaction process.
(3) Based on the nonequilibrium characteristic of low-temperature plasma reaction, the functionalization modification process adopted by the invention does not need to follow chemical reaction thermodynamics, so that the functionalization modification of MOFs has very wide selection and regulation space.
(4) The invention adopts organic micromolecules containing target functional groups as the functionalized modifier, the modifier is economical and easy to obtain and has rich sources, the functionalized modification of MOFs can be realized by a low-temperature plasma reaction process which is simple, direct and quick to start at room temperature and normal pressure, the range of the modifiable functional groups is wide, the universality is high, and the industrial cost is greatly reduced. Has very wide industrial application prospect.
In conclusion, the invention adopts the low-temperature plasma technology and carries out the functionalized modification on the MOFs in a gas-solid reaction mode. Compared with the traditional chemical modification method, the functionalization modification of the MOFs by the low-temperature plasma does not need to consider the problems of reaction thermodynamic limitation and the like, so that the functionalization modification range of the MOFs is very wide. The MOFs functionalization modification initiated by the low-temperature plasma technology requires short preparation time, is low in energy consumption, is economic and environment-friendly, and can completely maintain the characteristic crystal structure and regular pore structure of the MOFs. Can provide important material basis for the functional research and application of MOFs, and has wide application prospect.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention. The materials and instruments used in the following examples are commercially available unless otherwise specified.
Example 1:
the invention discloses a method for modifying MOFs materials by low-temperature plasmas, which comprises the following steps:
the method comprises the steps of placing 0.10g of MOFs material in a discharge reaction zone of a low-temperature plasma reactor, wherein the MOFs material is UiO-66, enabling argon gas with the flow rate of 50mL/min to pass through a double-neck flask filled with a liquid modifier, enabling the liquid modifier to be liquid at room temperature or be heated into a liquid organic reagent through an oil bath with the temperature not higher than 100 ℃, enabling the liquid modifier to be shown in table 1, enabling saturated steam carrying the modifier to enter the discharge reaction zone of the low-temperature plasma reactor, starting a low-temperature plasma power supply, and carrying out low-temperature plasma discharge reaction at room temperature and normal pressure, wherein the discharge mode is dielectric barrier discharge, the discharge power is 1.2W, and the reaction time is 20min. Saturated steam of a modifier carried by argon is activated under the condition of low-temperature plasma to generate a large number of active free radicals, the free radicals and a benzene ring on an organic connecting group (terephthalic acid) of the UiO-66 generate free radical substitution reaction, and when hydroquinone, triethylamine, 2-hydroxyethylamine and 3-hydroxypropionic acid are respectively used as modifiers, the UiO-66 modified by 2,5-dihydroxyphenyl, 1- (diethylamino) ethyl, 2-amino-1-hydroxyethyl and 3-hydroxypropionyl is respectively obtained. The functionalized modified UiO-66 was dried in a vacuum oven at 120 ℃ under vacuum overnight.
In the embodiment, argon is firstly introduced into the double-mouth flask filled with the liquid modifier through the gas guide tube, the gas guide tube extends below the liquid level of the liquid modifier, and the gas outlet tube is positioned above the liquid level and is communicated with the low-temperature plasma reactor, so that the argon passing through the double-mouth flask carries saturated steam of the modifier to enter a plasma reaction area of the low-temperature plasma reactor.
The functionalized modified MOFs material prepared in the embodiment is used as a solid phase extraction adsorbent and is respectively applied to solid phase extraction of chlorpyrifos, profenofos and malathion in a citrus extract. Weighing 5g of citrus matrix at room temperature, wherein the adding concentration of the pesticide is 5mg/kg, taking 20mL of acetone as an extracting agent, adding 2mg of functionalized and modified MOFs into an extracting solution, carrying out vortex for 1min, carrying out centrifugal separation, eluting the functionalized and modified MOFs to adsorb enriched pesticide molecules by taking dichloromethane as an eluent, carrying out concentration and volume determination, carrying out instrument analysis, and investigating the influence of different modifying agents on the UiO-66 adsorption performance when the organophosphorus pesticide is extracted in a solid phase.
TABLE 1 influence of different modifiers on the adsorption Performance of functionalized UiO-66 for adsorbing organophosphorus
Example 2:
the invention discloses a method for modifying MOFs materials by low-temperature plasmas, which comprises the following steps:
the method comprises the steps of placing 0.10g of MOFs (metal-organic frameworks) in a discharge reaction zone of a low-temperature plasma reactor, wherein the MOFs is MIL-101, passing argon with the flow rate of 50mL/min through a double-neck flask filled with a liquid modifier, wherein the liquid modifier is an organic reagent which is liquid at room temperature or can be heated into the organic reagent by an oil bath with the temperature of not higher than 100 ℃, the specific modifier is shown in a table 2, saturated steam of the modifier carried by the argon enters the discharge reaction zone of the low-temperature plasma reactor, starting a low-temperature plasma power supply, and carrying out low-temperature plasma discharge reaction at room temperature and normal pressure, wherein the discharge mode is dielectric barrier discharge, the discharge power is 1.2W, and the reaction time is 20min. Saturated steam of a modifier carried by argon is activated under the condition of low-temperature plasma to generate a large number of active free radicals, the free radicals and a benzene ring on an organic connecting group (terephthalic acid) of MIL-101 undergo free radical substitution reaction, and when phenethylamine, p-toluidine, 1,2-cyclohexanediol and isopropanol are respectively used as modifiers, MIL-101 modified by 4- (2-aminoethyl) phenyl, 4-aminobenzyl, 1,2-dihydroxy-1-cyclohexyl and 2-hydroxy-2-propyl is respectively obtained. After the functionalized modification, MIL-101 was dried in a vacuum oven at 150 ℃ under vacuum overnight.
The functionalized and modified MOFs material prepared by the embodiment is used as a solid-phase extraction adsorbent and is respectively used for solid-phase extraction of different pyrethroid pesticides in grape extracting solution, wherein the pyrethroid pesticides include deltamethrin, cypermethrin, beta-cyfluthrin and bifenthrin. Weighing 5g of grape matrix at room temperature, wherein the pesticide addition concentration is 5mg/kg, taking 20mL of acetonitrile as an extracting agent, adding 2mg of functionalized modified MOFs into an extracting solution, carrying out vortex for 1min, carrying out centrifugal separation, eluting the functionalized modified MOFs to adsorb enriched pesticide molecules by taking acetone-n-hexane (V/V = 1/9) as an eluent, concentrating to a constant volume, carrying out instrument analysis, and investigating the influence of different modifying agents on the adsorption performance of MIL-101.
TABLE 2 influence of different modifying agents on the adsorption Performance of functionalized modified MIL-101 for pyrethroid pesticides
Example 3:
the invention discloses a method for modifying MOFs materials by low-temperature plasmas, which comprises the following steps:
the method comprises the steps of placing 0.10g of MOFs (metal-organic frameworks) in a discharge reaction zone of a low-temperature plasma reactor, wherein the MOFs is specifically ZIF-8, passing argon with the flow rate of 50mL/min through a double-neck flask filled with a liquid modifier, wherein the liquid modifier is an organic reagent which is liquid at room temperature or is heated into the organic reagent by an oil bath with the temperature of not higher than 100 ℃, the specific modifier is shown in a table 3, the argon enters the discharge reaction zone of the low-temperature plasma reactor with saturated steam of the modifier, starting a low-temperature plasma power supply, and carrying out low-temperature plasma discharge reaction at room temperature and normal pressure, wherein the plasma discharge mode is dielectric barrier discharge, the discharge power is 1.2W, and the reaction time is 20min. Saturated steam of a modifier carried by argon is activated under the condition of low-temperature plasma to generate a large number of active free radicals, the free radicals and imidazole rings on an organic connecting group (2-methylimidazole) of ZIF-8 undergo free radical substitution reaction, and when formic acid, acetic acid, benzoic acid and trifluoroacetic acid are respectively used as modifiers, ZIF-8 modified by formyl, acetyl, benzoyl and trifluoroacetyl is respectively obtained. The functionalized modified ZIF-8 was dried in a vacuum oven at 120 ℃ under vacuum overnight.
The functionalized modified MOFs material prepared in the embodiment is used as a solid phase extraction adsorbent and is respectively used for solid phase extraction of different neonicotinoid pesticides in acetonitrile extracting solution of rice, wherein the different neonicotinoid pesticides comprise imidacloprid, acetamiprid, pymetrozine and nitenpyram. Weighing 5g of rice matrix at room temperature, wherein the pesticide addition concentration is 5mg/kg, taking 20mL of acetonitrile as an extracting agent, adding 2mg of functionalized and modified MOFs into an extracting solution, carrying out vortex for 1min, carrying out centrifugal separation, eluting the functionalized and modified MOFs to adsorb enriched pesticide molecules by using methanol as an eluent, carrying out concentration and volume determination, carrying out instrument analysis, and investigating the influence of different modifiers on ZIF-8 adsorption performance.
TABLE 3 influence of different modifiers on the adsorption Performance of functionalized modified ZIF-8 for neonicotinoid pesticides
Example 4:
the invention discloses a method for modifying MOFs materials by low-temperature plasmas, which comprises the following steps:
placing 0.10g of MOFs (metal-organic frameworks) in a discharge reaction zone of a low-temperature plasma reactor, wherein the MOFs is UiO-66 specifically, passing argon gas with the flow rate of 50mL/min through a double-neck flask filled with a triethylamine modifier, enabling saturated steam carrying triethylamine in the argon gas to enter the discharge reaction zone of the low-temperature plasma reactor, starting a low-temperature plasma power supply, and performing low-temperature plasma discharge reaction at room temperature and normal pressure, wherein the discharge mode is shown in Table 4, the discharge power is 1.2W, and the reaction time is 20min. The triethylamine saturated steam carried by argon is activated under the condition of low-temperature plasma to generate a large amount of active free radicals, and the free radicals and benzene rings on an organic connecting group (terephthalic acid) of the UiO-66 undergo a free radical substitution reaction to obtain the 1- (diethylamino) ethyl modified UiO-66. The functionalized modified UiO-66 was dried in a vacuum oven at 120 ℃ under vacuum overnight.
The functionalized modified UiO-66 prepared in the above example was used as a solid phase extraction adsorbent for solid phase extraction of chlorpyrifos, profenofos and malathion in citrus extract. Weighing 5g of citrus matrix at room temperature, wherein the pesticide addition concentration is 5mg/kg, taking 20mL of acetone as an extracting agent, adding 2mg of functionalized modified MOFs into an extracting solution, carrying out vortex for 1min, carrying out centrifugal separation, eluting the functionalized modified MOFs by using dichloromethane as an eluent to adsorb enriched pesticide molecules, carrying out concentration and volume determination, carrying out instrument analysis, and investigating the influence of different low-temperature plasma discharge modes on the adsorption performance of the functionalized modified UO-66 when triethylamine is used as a modifier.
TABLE 4 influence of different discharge modes on the adsorption performance of functionalized UiO-66 for adsorbing organophosphorus pesticides
Example 5:
the invention discloses a method for modifying MOFs materials by low-temperature plasmas, which comprises the following steps:
the method comprises the steps of placing 0.10g of MOFs (metal-organic frameworks) in a discharge reaction zone of a low-temperature plasma reactor, wherein the MOFs is specifically MIL-101, enabling argon with the flow rate of 50mL/min to pass through a double-neck flask filled with a phenylethylamine modifier, enabling the argon carrying saturated vapor of the phenylethylamine to enter the discharge reaction zone of the low-temperature plasma reactor, starting a low-temperature plasma power supply, and carrying out low-temperature plasma discharge reaction at room temperature and normal pressure, wherein the plasma discharge mode is dielectric barrier discharge, the discharge power is shown in table 5, and the reaction time is 20min. The phenylethylamine saturated steam carried by argon is activated under the condition of low-temperature plasma to generate a large amount of active free radicals, and the free radicals and a benzene ring on an organic connecting group (terephthalic acid) of the MIL-101 undergo a free radical substitution reaction to obtain the MIL-101 modified by 4- (2-aminoethyl) phenyl. After the functionalized modification, MIL-101 was dried in a vacuum oven at 150 ℃ under vacuum overnight.
The functionalized and modified MOFs material prepared in the embodiment is used as a solid-phase extraction adsorbent and is respectively used for solid-phase extraction of different pyrethroid pesticides in grape extract, wherein the pyrethroid pesticides comprise deltamethrin, cypermethrin, beta-cyfluthrin and bifenthrin. Weighing 5g of grape matrix at room temperature, wherein the pesticide addition concentration is 5mg/kg, taking 20mL of acetonitrile as an extractant, adding 2mg of functionalized MOFs into the extract, carrying out vortex for 1min, carrying out centrifugal separation, eluting the functionalized MOFs by using acetone-n-hexane (V/V = 1/9) as an eluent to adsorb enriched pesticide molecules, carrying out concentration and volume fixing, carrying out instrument analysis, and investigating the influence of plasma discharge power on the functionalized modified MIL-101 adsorption performance.
TABLE 5 influence of discharge power on adsorption of pyrethroid pesticides by functionalized modified MIL-101
Example 6:
the invention discloses a method for modifying MOFs materials by low-temperature plasmas, which comprises the following steps:
the method comprises the steps of placing 0.10g of MOFs (metal-organic frameworks) in a discharge reaction zone of a low-temperature plasma reactor, wherein the MOFs is specifically ZIF-8, enabling argon with saturated benzoic acid steam to enter the discharge reaction zone of the low-temperature plasma reactor after the argon with a certain flow rate passes through a double-neck flask filled with a benzoic acid modifier, starting a low-temperature plasma power supply to perform low-temperature plasma discharge reaction at room temperature and normal pressure, wherein the plasma discharge mode is dielectric barrier discharge, the discharge power is 1.2W, and the reaction time is 20min. Benzoic acid saturated steam carried by argon is activated under the condition of low-temperature plasma to generate a large number of active free radicals, and the free radicals and imidazole rings on an organic connecting group (2-methylimidazole) of the ZIF-8 undergo a free radical substitution reaction to obtain the ZIF-8 modified by benzoyl. The functionalized modified ZIF-8 was dried in a vacuum oven at 120 ℃ under vacuum overnight.
The functionalized and modified metal organic framework material prepared in the embodiment is used as a solid phase extraction adsorbent for solid phase extraction of neonicotinoid pesticides in a rice extraction solution, and comprises imidacloprid, acetamiprid, pymetrozine and nitenpyram. Weighing 5g of rice matrix at room temperature, wherein the pesticide addition concentration is 5mg/kg, taking 20mL of acetonitrile as an extractant, adding 2mg of functionalized modified MOFs into the extract, carrying out vortex for 1min, carrying out centrifugal separation, eluting the functionalized modified MOFs to adsorb enriched pesticide molecules by using methanol as an eluent, carrying out concentration and volume determination, carrying out instrument analysis, and investigating the influence of argon flow rate on the adsorption performance of the functionalized modified ZIF-8 in the plasma reaction process.
TABLE 6 influence of argon flow Rate on the adsorption Performance of functionalized modified ZIF-8 for neonicotinoid pesticides
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (9)
1. A method for modifying MOFs materials by low-temperature plasmas is characterized by comprising the following steps: and under the condition of air tightness, passing argon through a liquid modifier, and enabling saturated steam carrying the liquid modifier with the argon to perform low-temperature plasma discharge reaction with MOFs, wherein the liquid modifier is an organic reagent which is liquid at room temperature or an organic reagent which is liquid under the heating condition of an oil bath at the temperature of not higher than 100 ℃, the low-temperature plasma discharge reaction is performed under the conditions of room temperature and normal pressure, the discharge power is 0.5W-1.5W, and after the plasma reaction is finished, the functionalized and modified MOFs are obtained.
2. The method according to claim 1, characterized in that said MOFs comprise one or more MOFs of the MIL series, the UiO series, the ZIF series and the HKUST series.
3. The method for modifying MOFs materials according to claim 1, wherein said organic agent comprises one or more of phenol, alcohol, organic amine, carboxylic acid and hydroxycarboxylic acid.
4. The method for modifying the MOFs according to claim 1, wherein the time for the low temperature plasma discharge reaction is 20-60 min.
5. The method for modifying the MOFs according to any one of claims 1 to 4, wherein the low temperature plasma discharge mode comprises one of glow discharge, dielectric barrier discharge and pulse discharge.
6. The method for low-temperature plasma modification of MOFs materials according to any of the claims 1 to 4, wherein said flow rate of argon is comprised between 20 and 100mL/min.
7. The method for low-temperature plasma modification of MOFs according to any one of claims 1 to 4, wherein after the plasma reaction is completed, vacuum drying is carried out at 120 ℃ to 150 ℃ overnight.
8. Use of the functionalized modified MOFs prepared by the method of low temperature plasma modification of MOFs materials according to any one of claims 1 to 7 as solid phase extraction adsorbents for the adsorption of enriched pesticide molecules in complex matrices.
9. The use of claim 8, wherein the complex substrate comprises a fruit, vegetable, grain, meat, egg, seafood, soil or environmental water, and the pesticide molecule comprises one or more of an insecticide, a fungicide and a herbicide.
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